CN108431064B - Block copolymer, dispersant and pigment dispersion composition - Google Patents

Block copolymer, dispersant and pigment dispersion composition Download PDF

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CN108431064B
CN108431064B CN201780004006.8A CN201780004006A CN108431064B CN 108431064 B CN108431064 B CN 108431064B CN 201780004006 A CN201780004006 A CN 201780004006A CN 108431064 B CN108431064 B CN 108431064B
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CN108431064A (en
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清水达彦
梅本光
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Otsuka Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

The present invention provides a block copolymer which can be used as a dispersant and has excellent heat resistance. A block copolymer comprising an A block containing a structural unit derived from a vinyl monomer having an acidic group and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). In the formulae (1) and (2), R11、R12、R13、R21And R22Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R11、R12And R13Two or more of them may bond to each other and form a cyclic structure. R21And R22May bond to each other and form a cyclic structure. X1And X2Represents a divalent linking group. R14And R23Represents a hydrogen atom or a methyl group. Y is‑Represents at least one selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions.

Description

Block copolymer, dispersant and pigment dispersion composition
Technical Field
The present invention relates to a block copolymer, a dispersant and a pigment-dispersion composition.
Background
Conventionally, in the production of color filters used in liquid crystal displays and the like, methods for applying a coloring material to a substrate include a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like. Among them, the pigment dispersion method is widely used from the viewpoint of spectral characteristics, durability, pattern shape and accuracy. In the pigment dispersion method, for example, a coating film composed of a pigment dispersion composition in which a pigment, a dispersant, and a dispersion medium (solvent) are mixed is formed on a substrate, and is exposed to light through a photomask having a desired pattern shape, followed by alkali development.
In the manufacture of a liquid crystal display, a pattern of a coloring material is formed, a transparent electrode for driving liquid crystal is formed thereon by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a fixed direction is formed thereon. In order to sufficiently obtain the properties of these transparent electrodes and alignment films, the formation of these transparent electrodes and alignment films is generally performed at a high temperature of 200 ℃ or higher. However, if a resin-type dispersant is used in a large amount in the pigment dispersion composition, problems of heat resistance such as a decrease in contrast and a change in chromaticity of the color filter occur before and after the process involving high heat.
Therefore, resin-type dispersants for improving heat resistance have been proposed. For example, patent document 1 discloses that an a-B block copolymer composed of an a block having a quaternary ammonium salt group in a side chain and a B block having no quaternary ammonium salt group is used as a pigment dispersant for a color filter in order to obtain a color filter having excellent heat resistance (see claim 1, paragraphs 0049 to 0058 of patent document 1).
Further, patent document 2 discloses that an a-B block copolymer composed of an a block having an acidic group in a side chain and a B block having an amino group or a quaternary ammonium salt group in a side chain is used as a pigment dispersant to improve coating properties, long-term storage stability and alkali developability (see claims 1, 0031 to 0034, and 0038 to 0040 of patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012-068559
Patent document 2: japanese patent laid-open publication No. 2013-203887
Disclosure of Invention
Problems to be solved by the invention
Resin type dispersants having improved heat resistance have been proposed in the past, but there is a problem that the heat resistance of resin type dispersants is not sufficient. The present invention has been made in view of the above circumstances, and an object thereof is to provide a block copolymer which is useful as a dispersant and has excellent heat resistance.
Means for solving the problems
The block copolymer of the present invention capable of solving the above problems is characterized by having an a block containing a structural unit derived from a vinyl monomer having an acidic group and a B block containing a structural unit represented by general formula (1) and a structural unit represented by general formula (2).
Figure BDA0001659759100000021
(in the formula (1), R11、R12And R13Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R11、R12And R13Two or more of them may bond to each other and form a cyclic structure. X1Represents a divalent linking group. R14Represents a hydrogen atom or a methyl group. Y is-Represents at least one selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions. )
Figure BDA0001659759100000022
(in the formula (2), R21And R22Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R21And R22Can bond with each other and form a ring structure。X2Represents a divalent linking group. R23Represents a hydrogen atom or a methyl group. )
Existing polymers with quaternary ammonium salt groups generally use halide anions as counterions to the quaternary ammonium cations. It is considered that such a polymer containing a halogen anion is inferior in heat resistance because a reaction for eliminating a counter ion occurs in a high-temperature atmosphere. The block copolymer of the present invention has excellent heat resistance because the counter ion of the quaternary ammonium cation in the B block is an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, or an aromatic carboxylic acid anion. Further, the block copolymer of the present invention has an a block having an acidic group and a B block having a specific structure, and thus can be used as a dispersant.
The block copolymer is preferably an A-B type block copolymer. In the block copolymer, the content of the structural unit derived from the vinyl monomer having an acidic group in 100 mass% of the a block is preferably 2 to 20 mass%. In the block copolymer, the content of the structural unit represented by the general formula (1) in 100% by mass of the B block is preferably 30% by mass to 85% by mass. The content of the a block in 100 mass% of the block copolymer is preferably 35 to 85 mass%.
The present invention also includes a first composition containing the block copolymer and a second composition obtained by washing and drying the first composition. The molecular weight distribution (PDI) of the block copolymer contained in the first composition is preferably 2.0 or less. In addition, a dispersant containing the block copolymer, the first composition or the second composition is also included in the present invention. Further, the present invention also includes a pigment dispersion composition containing the dispersant, pigment and dispersion solvent. Such a composition includes a pigment dispersion composition for a color filter.
The method for producing a block copolymer of the present invention is characterized by comprising the steps of: a step (A) for preparing a precursor of a block copolymer, wherein the precursor of the block copolymer has an A block and a B block, the A block contains a structural unit derived from a vinyl monomer having an acidic group, and the B block contains a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3); and (B) a step of obtaining a block copolymer by allowing an alkali metal salt of at least one member selected from the group consisting of aromatic dicarboxylic acid imides, aromatic sulfonic acids, aromatic phosphonic acids, and aromatic carboxylic acids to act on the precursor of the block copolymer obtained in the step (a).
Figure BDA0001659759100000031
(in the formula (2), R21And R22Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R21And R22May bond to each other and form a cyclic structure. X2Represents a divalent linking group. R23Represents a hydrogen atom or a methyl group. )
Figure BDA0001659759100000041
(in the formula (3), R31、R32And R33Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R31、R32And R33Two or more of them may bond to each other and form a cyclic structure. X3Represents a divalent linking group. R34Represents a hydrogen atom or a methyl group. X-Represents a halogen anion. )
In the step (B), the counter ion of the quaternary ammonium cation can be easily exchanged from the halogen anion (anion exchange) to the aromatic dicarboxylic acid imide anion, the aromatic sulfonic acid anion, the aromatic phosphonic acid anion or the aromatic carboxylic acid anion by using the aromatic dicarboxylic acid imide, the aromatic sulfonic acid, the aromatic phosphonic acid or the alkali metal salt of the aromatic carboxylic acid.
In the anion exchange in the step (B), each ion is classified according to the theory of soft and hard acids and bases (HSAB). For example, halide ions (e.g., chloride ions) are classified as hard bases because of their large electronegativity and small polarizability. Alkali metal ions (e.g., potassium ions) are classified as hard acids. Aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions having an aromatic ring pi-electron system are considered to be classified as soft bases. The quaternary ammonium ions in the polymer are considered to be classified as soft acids. According to the HSAB theory, it is considered that the bond and the strength of the combination of an acid and a base having the same hardness as the soft acid and the soft base, and the hard acid and the hard base are strong. In the above anion exchange, it is considered that anion exchange is facilitated by the formation of a bond and a strong ion pair.
In the production method, it is preferable that a precursor of the block copolymer is prepared by living radical polymerization in the step (a). The production method preferably includes a step (C) of washing the block copolymer obtained in the step (B) with water.
Effects of the invention
According to the present invention, a block copolymer which is useful as a dispersant and has excellent heat resistance can be provided.
Detailed Description
An example of a preferred embodiment of the present invention will be described below. The following embodiments are merely examples. The present invention is not limited to the following embodiments.
<1 Block copolymer >
The block copolymer of the present invention is characterized by having an a block containing a structural unit derived from a vinyl monomer having an acidic group and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
In the present invention, "A block" may be interchanged with "A segment" and "B block" may be interchanged with "B segment". In the present invention, the "vinyl monomer" means a monomer having a carbon-carbon double bond in the molecule which can undergo radical polymerization. The "structural unit derived from a vinyl monomer" means a structural unit in which a carbon-carbon double bond capable of radical polymerization of a vinyl monomer is polymerized to form a carbon-carbon single bond. "(meth) propenyl" means "at least one of propenyl and methylpropenyl". "(meth) acrylate" means "at least one of acrylate and methacrylate". "(meth) acryloyl" means "at least one of acryloyl and methacryloyl".
The various constituent components and the like of the block copolymer of the present invention will be explained below.
(1.1A Block)
The a block is a polymer block having structural units derived from a vinyl monomer having an acidic group. It is considered that the acid group of the a block facilitates alkali development. Therefore, the block copolymer is preferably used for a pigment-dispersion composition for color filters preferably used for the production of color filters using alkali development.
Examples of the acidic group include a carboxyl group (-COOH) and a sulfonic acid group (-SO)3H) Phosphoric acid group (-
OPO3H2) Phosphonic acid group (-PO)3H2) Phosphinic acid group (-PO)2H2). The a block may have only one structural unit derived from a vinyl monomer having an acidic group, or may have two or more structural units derived from a vinyl monomer having an acidic group.
The vinyl monomer having an acidic group is preferably at least one selected from a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, or a vinyl monomer having a phosphoric acid group. Among them, preferred is at least one selected from the group consisting of a (meth) acryl-based monomer having a carboxyl group, a (meth) acryl-based monomer having a sulfonic acid group, and a (meth) acryl-based monomer having a phosphoric acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid; monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride or phthalic anhydride with a vinyl monomer having a hydroxyl group (preferably hydroxyalkyl (meth) acrylate), such as 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate or 2- (meth) acryloyloxyethyl phthalate; crotonic acid, maleic acid, itaconic acid, and the like.
Examples of the vinyl monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, disulfonic acid ethyl (meth) acrylate, methylpropylsulfonic acid (meth) acrylamide, and sulfoethyl (meth) acrylamide.
Examples of the vinyl monomer having a phosphoric acid group include 2- (phosphoryloxy) ethyl (meth) acrylate and the like.
The content of the structural unit derived from the vinyl monomer having an acidic group in 100 mass% of the a block is preferably 2 mass% or more, more preferably 5 mass% or more, further preferably 7 mass% or more, preferably 20 mass% or less, more preferably 18 mass% or less, and further preferably 16 mass% or less. When the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate at the time of neutralization with an alkali in alkali development is high, and when it is 20% by mass or less, the hydrophilicity is not excessively high, and the formation of disordered pixels can be suppressed.
The A block may also have other structural units than those derived from a vinyl monomer having an acidic group. The other structural units that may be contained in the a block are not particularly limited as long as they are structural units formed from a vinyl monomer that can be copolymerized with both a vinyl monomer having an acidic group and a vinyl monomer forming the B block described later. The vinyl monomers of other structural units capable of forming the A block may be used alone or in combination of two or more.
Specific examples of the vinyl monomer capable of forming the other structural unit of the A block include α -olefins, aromatic vinyl monomers, heterocyclic ring-containing vinyl monomers, vinyl amides, vinyl carboxylates, dienes, (meth) acryl monomers, and the like. These vinyl monomers may have a hydroxyl group or an epoxy group.
As the α -olefin, 1-hexene, 1-octene, 1-decene and the like are exemplified.
Examples of the aromatic vinyl monomer include styrene, α -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene and 1-vinylnaphthalene.
Examples of the heterocycle-containing vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, and 4-vinylpyridine.
Examples of the vinyl amide include N-vinylformamide, N-vinylacetamide, and N-vinyl-epsilon-caprolactam.
Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, and vinyl benzoate.
The dienes include butadiene, isoprene, 4-methyl-1, 4-hexadiene, 7-methyl-1, 6-octadiene and the like.
Examples of the (meth) acryl-based monomer include (meth) acrylates having a chain alkyl group (a linear alkyl group or a branched alkyl group); (meth) acrylate having a cyclic alkyl group (monocyclic structure); (meth) acrylate having an aromatic ring group; (meth) acrylamide; (meth) acrylate having a polyethylene glycol structural unit; a (meth) acrylate having a hydroxyl group; caprolactone adducts of (meth) acrylates having hydroxyl groups; a (meth) acrylate having an alkoxy group; and (meth) acrylates having cyclic ether groups.
Examples of the (meth) acrylate having a chain alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Examples of the (meth) acrylate having a cyclic alkyl group include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate. Examples of the (meth) acrylate having an aromatic ring group include benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.
Examples of the (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide. Examples of the (meth) acrylate having a polyethylene glycol structural unit include polyethylene glycol (n ═ 1 to 5) methyl ether (meth) acrylate, polyethylene glycol (n ═ 1 to 5) ethyl ether (meth) acrylate, polyethylene glycol (n ═ 1 to 5) propyl ether (meth) acrylate, polypropylene glycol (n ═ 1 to 5) methyl ether (meth) acrylate, polypropylene glycol (n ═ 1 to 5) ethyl ether (meth) acrylate, and polypropylene glycol (n ═ 1 to 5) propyl ether (meth) acrylate.
Examples of the (meth) acrylate having a hydroxyl group include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the caprolactone adduct of a (meth) acrylate having a hydroxyl group include a 1-mole caprolactone adduct of 2-hydroxyethyl (meth) acrylate, a 2-mole caprolactone adduct of 2-hydroxyethyl (meth) acrylate, a 3-mole caprolactone adduct of 2-hydroxyethyl (meth) acrylate, a 4-mole caprolactone adduct of 2-hydroxyethyl (meth) acrylate, and a 5-mole caprolactone adduct of 2-hydroxyethyl (meth) acrylate.
Examples of the (meth) acrylate having an alkoxy group include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
Examples of the (meth) acrylate having a cyclic ether group include glycidyl (meth) acrylate, tetrahydrofuran (meth) acrylate, (meth) acryloylmorpholine, 2- (4-morpholino) ethyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2- [ (2-tetrahydropyranyl) oxy) ] ethyl (meth) acrylate, and 1, 3-dioxane- (meth) acrylate.
The vinyl monomer capable of forming another structural unit that can be contained in the a block is preferably a (meth) acryl-based monomer, and more preferably at least one selected from the group consisting of a (meth) acrylate having a chain alkyl group, a (meth) acrylate having an aromatic ring group, a (meth) acrylate having a polyethylene glycol structural unit, a (meth) acrylate having a hydroxyl group, a caprolactone adduct of a (meth) acrylate having a hydroxyl group, and a (meth) acrylate having a cyclic ether group. The vinyl monomers that can be used for the A block may be used singly or in combination.
When the a block has a structural unit derived from at least one vinyl monomer selected from the group consisting of a (meth) acrylate having a chain alkyl group, a (meth) acrylate having a cyclic alkyl group, and a (meth) acrylate having an aromatic ring group, the total content of these structural units in 100% by mass of the a block is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, preferably 98% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.
When the a block has a structural unit derived from at least one vinyl monomer selected from the group consisting of (meth) acrylamide, (meth) acrylate having a polyethylene glycol structural unit, a (meth) acrylate having a hydroxyl group, a caprolactone adduct of a (meth) acrylate having a hydroxyl group, a (meth) acrylate having an alkoxy group, and a (meth) acrylate having a cyclic ether group, the total content of these structural units in 100 mass% of the a block is preferably 2 mass% or more, more preferably 5 mass% or more, further preferably 10 mass% or more, preferably 70 mass% or less, more preferably 65 mass% or less, and further preferably 60 mass% or less.
Furthermore, the a block preferably has no amino group. That is, the vinyl monomer constituting the a block preferably does not contain a vinyl monomer having an amino group. If a large amount of amino groups are present in the A block, the pigment is adsorbed on both the A block and the B block when used as a pigment dispersant, and the dispersibility of the pigment is lowered. The content of the structural unit derived from the vinyl monomer having an amino group in the a block is preferably 2% by mass or less, more preferably 1% by mass or less, further preferably 0.1% by mass or less, and most preferably 0% by mass.
When the a block contains two or more kinds of structural units, the various structural units contained in the a block may be contained in the a block in any form such as random copolymerization, block copolymerization, etc., and from the viewpoint of uniformity, the random copolymerization is preferably contained. For example, the a block may be formed from the following copolymers: the copolymer has a structural unit composed of an a1 block and a structural unit composed of an a2 block.
(1.2B Block)
The B block is a polymer block having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). The B block has a quaternary ammonium salt group in addition to the tertiary amine group, and thus is considered to have high affinity with the pigment.
(1.2.1 structural Unit represented by the general formula (1))
The structural unit represented by the general formula (1) has a quaternary ammonium salt in the structure, and has at least one selected from the group consisting of an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, and an aromatic carboxylic acid anion as an anion component thereof. The B block may have only one or two or more kinds of the structural units represented by the general formula (1).
Figure BDA0001659759100000091
(in the formula (1), R11、R12And R13Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R11、R12And R13Two or more of them may bond to each other and form a cyclic structure. X1Represents a divalent linking group. R14Represents a hydrogen atom or a methyl group. Y is-Represents at least one selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions. )
The R is11～R13The chain hydrocarbon group includes both straight-chain and branched-chain hydrocarbon groups. The R is11～R13Examples of the substituent of the chain hydrocarbon group include a halogen group, an alkoxy group, and a benzoyl group (-COC)6H5) Hydroxyl groups, and the like. The R is11～R13Examples of the substituent of the cyclic hydrocarbon group include a chain alkyl group, a halogen atom, an alkoxy group, and a hydroxyl group.
The R is11～R13The radicals indicated may preferably haveThe substituent is an alkyl group having 1 to 4 carbon atoms or an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and more preferably a methyl group, an ethyl group, a propyl group, or a benzyl group (-CH)2C6H5)。
The R is11～R13Examples of the cyclic structure formed by bonding two or more members of (a) to (b) include a five-to seven-membered nitrogen-containing heteromonocyclic ring and a condensed ring formed by condensing two nitrogen-containing heteromonocyclic rings. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably is a saturated ring. Specific examples thereof include those represented by the following formulae (11-1), (11-2) and (11-3).
Figure BDA0001659759100000092
(in the general formulae (11-1), (11-2) and (11-3), R61Is R11～R13Any one of them. R62Represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5. m represents an integer of 0 to 4. n represents an integer of 0 to 4. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R exist62May be the same or different. )
A divalent linking group X in the formula (1)1Examples thereof include methylene, alkylene having 2 to 10 carbon atoms, arylene, -CONH-R15-radical, -COO-R16-radical (wherein, R15And R16A single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms. Divalent linking group X1preferably-COO-R16A radical, more preferably-COO-R17-radical (wherein, R17A methylene group or an alkylene group having 2 to 4 carbon atoms).
In the above general formula (1), the counterion Y-Represents at least one selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions. Wherein the counter ion Y-Preferably, the anion of aromatic dicarboxylic acid imide and the anion of aromatic sulfonic acid are used.
The aromatic dicarboxylic acid imide anion is an anion of aromatic dicarboxylic acid imide, and is an anion obtained by removing a proton from a nitrogen constituting dicarboxylic acid imide. The aromatic dicarboxylic acid imide has an aromatic ring and an imide group (-C (═ O) NHC (═ O) -) directly bonded to the aromatic ring in the molecule. The two ends of the imide group may be bonded to one aromatic ring or bonded to different aromatic rings. The aromatic dicarboxylic acid imide anion is preferably an anion represented by the general formula (12).
Figure BDA0001659759100000101
(in the general formula (12), Ring A represents an optionally substituted aromatic ring.)
In the general formula (12), the aromatic ring constituting the ring A means a ring structure having aromatic properties. The aromatic ring includes any of a monocyclic ring and a fused ring. The monocyclic ring is preferably a five-or six-membered ring, and a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring is suitable. The condensed ring is preferably a 2-5 condensed ring, and is suitably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring. The substituent that the aromatic ring may have includes an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
Aromatic dicarboxylic acid imide anion, which may be mentioned 1, 3-dioxo-1, 3-dihydro-2H-isoindol-2-anion (formula (12-1)); 1, 3-dioxo-1, 3-dihydro-2H-benzo [ f ] isoindol-2-anion (formula (12-2)); 1, 3-dioxo-1, 3-dihydro-2H-benzo [ g ] isoindol-2-anion (formula (12-3)); 5-phenyl-1, 3-dioxo-1, 3-dihydro-2H-isoindol-2-anion (formula (12-4)); 1, 3-dioxo-1, 3-dihydro-2H-naphthalene [2, 3-f ] isoindol-2-anion (formula (12-5)); 1, 3-dioxo-1, 3-dihydro-2H-naphthalene [2, 3-g ] isoindol-2-anion (formula (12-6)); 1, 3-dioxo-1, 3-dihydro-2H-dibenzo [ e, g ] isoindol-2-anion (formula (12-7)), and the like.
Figure BDA0001659759100000111
The aromatic sulfonic acid anion is an anion of an aromatic sulfonic acid. The aromatic sulfonic acid has an aromatic ring and a sulfonic acid group directly bonded to the aromatic ring in the molecule. The aromatic sulfonic acid anion is preferably an anion represented by the following formula (13).
Figure BDA0001659759100000112
(in the general formula (13), Ar represents an optionally substituted aromatic ring.)
In the general formula (13), the aromatic ring constituting Ar means a ring structure having aromaticity. The aromatic ring includes any of a monocyclic ring and a fused ring. The monocyclic ring is preferably a five-or six-membered ring, and a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring is suitable. The condensed ring is preferably a 2-5 condensed ring, and is suitably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring. The substituent that the aromatic ring may have includes an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
Aromatic sulfonic acid anions, for example, benzenesulfonic acid anion (formula (13-1)); 1-naphthalenesulfonic acid anion (formula (13-2)); 2-naphthalenesulfonic acid anion (formula (13-3)); 4-biphenylsulfonic acid anion (formula (13-4)); 2-anthracenesulfonic acid anion (formula (13-5)); 1-anthracenesulfonic acid anion (formula (13-6)); 3-phenanthrene sulfonic acid anion (formula (13-7)); a p-styrenesulfonic acid anion (formula (13-8)); p-toluenesulfonic acid anion (formula (13-9)), and the like.
Figure BDA0001659759100000121
The aromatic phosphonic acid anion is the anion of an aromatic phosphonic acid. The aromatic phosphonic acid has an aromatic ring and a phosphonic acid group directly bonded to the aromatic ring in the molecule. The aromatic phosphonic acid anion is preferably an anion represented by the following formula (14).
Figure BDA0001659759100000122
(in the general formula (14), Ar represents an optionally substituted aromatic ring.)
In the general formula (14), the aromatic ring constituting Ar means a ring structure having aromatic properties. The aromatic ring includes any of a monocyclic ring and a fused ring. The monocyclic ring is preferably a five-or six-membered ring, and a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring is suitable. The condensed ring is preferably a 2-5 condensed ring, and is suitably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring. The substituent that the aromatic ring may have includes an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
Aromatic phosphonic acid anions, for example, phenylphosphonic acid anion (formula (14-1)); 1-naphthalene phosphonic acid anion (formula (14-2)); 2-naphthylphosphonic acid anion (formula (14-3)); 4-biphenylphosphonic acid anion (formula (14-4)); 2-anthracenylphosphonic acid anion (formula (14-5)); 1-anthracenylphosphonic acid anion (formula (14-6)); 3-phenanthrene phosphonate anion (formula (14-7)), and the like.
Figure BDA0001659759100000131
The aromatic carboxylic acid anion is an anion of an aromatic carboxylic acid. The aromatic carboxylic acid has an aromatic ring and a carboxyl group directly bonded to the aromatic ring in the molecule. The aromatic carboxylic acid anion is preferably an anion represented by the following formula (15).
Figure BDA0001659759100000132
(in the general formula (15), Ar represents an optionally substituted aromatic ring.)
In the general formula (15), the aromatic ring constituting Ar means a ring structure having aromaticity. The aromatic ring includes any of a monocyclic ring and a fused ring. The monocyclic ring is preferably a five-or six-membered ring, and a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring is suitable. The condensed ring is preferably a 2-5 condensed ring, and is suitably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring. The substituent that the aromatic ring may have includes an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
Aromatic carboxylic acid anions, such as benzoic acid anion (formula (15-1)); 1-naphthoic acid anion (formula (15-2)); 2-naphthoic acid anion (formula (15-3)); 4-biphenylcarboxylic acid anion (formula (15-4)); 2-anthracenecarboxylic acid anion (formula (15-5)); 1-anthracenecarboxylic acid anion (formula (15-6)); 3-phenanthrenecarboxylic acid anion (formula (15-7)); p-vinylbenzoic acid anion (formula (15-8)); p-methylbenzoate anion (formula (15-9)), and the like.
Figure BDA0001659759100000141
The content of the structural unit represented by the general formula (1) in 100% by mass of the B block is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less. It is considered that by setting the content of the structural unit represented by the general formula (1) within this range, the pigment has high affinity.
(1.2.2 structural units represented by the general formula (2))
The structural unit represented by the general formula (2) has a tertiary amine structure. The B block may have only one or two or more kinds of the structural units represented by the general formula (2).
Figure BDA0001659759100000142
(in the formula (2), R21And R22Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R21And R22May bond to each other and form a cyclic structure. X2Represents a divalent linking group. R23Represents a hydrogen atom or a methyl group. )
The R is21Or R22The chain hydrocarbon group includes both straight-chain and branched-chain hydrocarbon groups. The R is21Or R22Examples of the substituent of the chain hydrocarbon group include a halogen group, an alkoxy group, a benzoyl group, and a hydroxyl group. The R is21Or R22Shown as being cyclicExamples of the substituent group of the hydrocarbon group include a chain alkyl group, a halogen group, an alkoxy group, and a hydroxyl group.
The R is21Or R22The group is preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and more preferably a methyl group, an ethyl group, a propyl group, or a benzyl group.
The R is21Or R22Examples of the bond and the cyclic structure include a five-to seven-membered nitrogen-containing heteromonocyclic ring or a condensed ring in which two nitrogen-containing heteromonocyclic rings are condensed. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably is a saturated ring. Specific examples thereof include those represented by the following formulae (21-1), (21-2) and (21-3).
Figure BDA0001659759100000151
(in the general formulae (21-1), (21-2) and (21-3), R71Represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5. m represents an integer of 0 to 4. n represents an integer of 0 to 4. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R exist71May be the same or different. )
The divalent linking group X in the above general formula (2)2Examples thereof include methylene, alkylene having 2 to 10 carbon atoms, arylene, -CONH-R24-radical, -COO-R25-radical (wherein, R24And R25A single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms), preferably-COO-R25A radical, more preferably-COO-R26-radical (wherein, R26A methylene group or an alkylene group having 2 to 4 carbon atoms).
The content of the structural unit represented by the general formula (2) in 100% by mass of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, preferably 70% by mass or less, more preferably 65% by mass or less, and further preferably 60% by mass or less. It is considered that by setting the content of the structural unit represented by the general formula (2) within this range, the pigment has high affinity.
The B block may have only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may contain other structural units. From the viewpoint of maintaining the affinity for the pigment, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. The B block preferably contains substantially no structural unit derived from a vinyl monomer having an acidic group, which the a block has. That is, the content of the structural unit derived from the vinyl monomer having an acidic group in the a block in 100 mass% of the B block is preferably 5 mass% or less, and more preferably 2 mass% or less.
Specific examples of the vinyl monomer capable of forming the other structural unit of the B block include the same vinyl monomers as those listed as specific examples of the vinyl monomer capable of forming the other structural unit of the A block.
When the B block contains two or more kinds of structural units, the various structural units contained in the B block may be contained in the B block in any form of random copolymerization, block copolymerization, or the like, and from the viewpoint of uniformity, the random copolymerization is preferably contained. For example, the B block may be formed of a copolymer having structural units consisting of the B1 block and structural units consisting of the B2 block.
(1.3 Block copolymer)
The structure of the block copolymer of the present invention is preferably a linear block copolymer. The linear block copolymer may have any structure (arrangement), but from the viewpoint of physical properties of the linear block copolymer or physical properties of the composition, it is preferable that the linear block copolymer has a structure selected from the group consisting of (A-B)mType, (A-B)m-type A, (B-A)mA copolymer having at least one structure of the group consisting of B-type (m is an integer of 1 or more, for example, an integer of 1 to 3). Among them, the diblock copolymer represented by A-B is preferable from the viewpoints of handling property at the time of processing and physical properties of the composition. Through the construction shown as A-BThe diblock copolymer according to (1), in which the structural unit derived from a vinyl monomer having an acidic group in the a block, the structural unit derived from a vinyl monomer having a tertiary amine group in the B block, and the structural unit derived from a vinyl monomer having a quaternary ammonium salt group are concentrated, is considered to effectively act on a pigment, a solvent, and an adhesive resin (alkali-soluble resin) as appropriate.
The content of the a block in 100 mass% of the entire block copolymer is preferably 35 mass% or more, more preferably 40 mass% or more, further preferably 45 mass% or more, preferably 85 mass% or less, more preferably 80 mass% or less, further preferably 75 mass% or less. The content of the B block in 100 mass% of the entire block copolymer is preferably 15 mass% or more, more preferably 20 mass% or more, further preferably 25 mass% or more, preferably 65 mass% or less, more preferably 60 mass% or less, further preferably 55 mass% or less. By adjusting the content of the a block and the B block within the above range, the heat resistance and the dispersibility when used as a dispersant can be achieved in a well-balanced manner.
<2 first composition of Block copolymer >
The first composition of the present invention contains the above-mentioned block copolymer. The first composition contains other components than the above-mentioned block copolymer. The other components may be impurities resulting from the method for producing the block copolymer. For example, when a quaternizing agent described later or an alkali metal salt of at least one selected from the group consisting of an aromatic dicarboxylic acid imide, an aromatic sulfonic acid, an aromatic phosphonic acid, and an aromatic carboxylic acid is used for producing the block copolymer, a halogen component derived from the quaternizing agent or an alkali metal component derived from an alkali metal salt of an aromatic dicarboxylic acid imide or the like can be mentioned. It is preferable to remove impurities such as a salt (a salt formed by a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide) precipitated in the first composition by filtration.
The molecular weight of the block copolymer contained in the first composition is measured by a gel permeation chromatography (hereinafter referred to as "GPC") method. The weight average molecular weight (Mw) of the block copolymer is preferably 5000 or more, more preferably 6000 or more, further preferably 7000 or more, preferably 15000 or less, more preferably 12000 or less, further preferably 10000 or less. When the weight average molecular weight is within the above range, the dispersibility when used as a dispersant is better.
The molecular weight distribution (PDI) of the block copolymer contained in the first composition is preferably 2.0 or less, and more preferably 1.6 or less. In the present invention, the molecular weight distribution (PDI) is a value obtained from (the weight average molecular weight (Mw)) of the block copolymer/(the number average molecular weight (Mn) of the block copolymer). The smaller the PDI, the narrower the breadth of the molecular weight distribution, and the copolymer having a uniform molecular weight, and when this value is 1.0, the breadth of the molecular weight distribution is the narrowest. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.0, the block copolymer contains a copolymer having a small molecular weight or a copolymer having a large molecular weight.
From the viewpoint of pigment adsorption and pigment dispersibility, the amine value of the first composition is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, further preferably 30mgKOH/g or more, preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, and further preferably 100mgKOH/g or less.
The acid value of the first composition is preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, further preferably 15mgKOH/g or more, preferably 50mgKOH/g or less, more preferably 40mgKOH/g or less, further preferably 35mgKOH/g or less. By setting the acid value within this range, the block copolymer can suitably act on the binder resin (alkali-soluble resin) without impairing the affinity between the block copolymer and the pigment.
<3 second composition of Block copolymer >
The second composition of the present invention is obtained by washing and drying the first composition. The second composition obtained by washing with water and drying has a reduced content of salt (salt formed by the halogen component derived from the quaternizing agent and the alkali metal component derived from the alkali metal salt such as aromatic dicarboxylic acid imide). Similarly to the first composition, the second composition also contains impurities resulting from the method for producing the block copolymer. The first composition is a composition containing the block copolymer, and includes a reaction solution in synthesizing the block copolymer.
The block copolymer contained in the second composition may have a structural unit represented by general formula (1) or may not have a structural unit represented by general formula (1). The second composition contains other components than the block copolymer. Examples of the other components include aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid, and aromatic carboxylic acid. These aromatic dicarboxylic acid imides, aromatic sulfonic acids, aromatic phosphonic acids, and aromatic carboxylic acids may be anionic or alkali metal salts.
The molecular weight of the block copolymer contained in the second composition is measured according to the GPC method. The weight average molecular weight (Mw) of the block copolymer is preferably 5000 or more, more preferably 6000 or more, further preferably 7000 or more, preferably 15000 or less, more preferably 12000 or less, further preferably 10000 or less. When the weight average molecular weight is within the above range, the dispersing property when used as a dispersant becomes better.
The molecular weight distribution (PDI) of the block copolymer contained in the second composition is preferably 2.0 or less, and more preferably 1.6 or less. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.0, the block copolymer contains a copolymer having a small molecular weight or a copolymer having a large molecular weight.
From the viewpoint of the adsorption to the pigment and the pigment dispersibility, the amine value of the second composition is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, further preferably 30mgKOH/g or more, preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, further preferably 100mgKOH/g or less.
The acid value of the second composition is preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, further preferably 15mgKOH/g or more, preferably 50mgKOH/g or less, more preferably 40mgKOH/g or less, further preferably 35mgKOH/g or less.
The halogen anion content of the second composition is preferably 8000ppm or less, more preferably 6000ppm or less, and further preferably 4000ppm or less.
<4 preparation method of Block copolymer >
The method for producing a block copolymer of the present invention is characterized by comprising the steps of: a step (a) of preparing a precursor of a block copolymer, the precursor of the block copolymer having an a block containing a structural unit derived from a vinyl monomer having an acidic group and a B block containing a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (3); and (B) a step of obtaining a block copolymer by allowing an alkali metal salt of at least one member selected from the group consisting of aromatic dicarboxylic acid imides, aromatic sulfonic acids, aromatic phosphonic acids, and aromatic carboxylic acids to act on the precursor of the block copolymer obtained in the step (a). In the present invention, the "precursor of the block copolymer" refers to the block copolymer before anion exchange.
(4.1 Process (A))
In the step (a), a precursor of a block copolymer is prepared. The precursor of the block copolymer has an A block containing a structural unit derived from a vinyl monomer having an acidic group and a B block containing a structural unit represented by general formula (2) and a structural unit represented by general formula (3).
Figure BDA0001659759100000191
(in the formula (2), R21And R22Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R21And R22May bond to each other and form a cyclic structure. X2Represents a divalent linking group. R23Represents a hydrogen atom or a methyl group. )
R in the formula (2)21～R23And X2The same as those described in the above description of the (B block).
Figure BDA0001659759100000192
(in the formula (3), R31、R32And R33Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R31、R32And R33Two or more of them may bond to each other and form a cyclic structure. X3Represents a divalent linking group. R34Represents a hydrogen atom or a methyl group. X-Represents a halogen anion. )
The R is31～R33The chain hydrocarbon group includes both straight-chain and branched-chain hydrocarbon groups. The R is31～R33Examples of the substituent of the chain hydrocarbon group include a halogen group, an alkoxy group, a benzoyl group, and a hydroxyl group. The R is31～R33Examples of the substituent of the cyclic hydrocarbon group include a chain alkyl group, a halogen group, an alkoxy group, and a hydroxyl group.
The R is31～R33The group is preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and more preferably a methyl group, an ethyl group, a propyl group, or a benzyl group.
The R is31～R33Examples of the cyclic structure formed by bonding two or more members of (a) to (b) to each other include a five-to seven-membered nitrogen-containing heteromonocyclic ring and a condensed ring formed by condensing two nitrogen-containing heteromonocyclic rings. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably is a saturated ring. Specific examples thereof include those represented by the following formulae (31-1), (31-2) and (31-3).
Figure BDA0001659759100000201
(in the general formulae (31-1), (31-2) and (31-3), R81Is R31～R33Any one of them. R82Represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5. m represents an integer of 0 to 4. n represents an integer of 0 to 4. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R exist82May be respectively the same or different。)
The divalent linking group X in the above general formula (3)3Examples thereof include methylene, alkylene having 2 to 10 carbon atoms, arylene, -CONH-R35-radical, -COO-R36-radical (wherein, R35And R36A single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms), preferably-COO-R36A radical, more preferably-COO-R37-radical (wherein, R37A methylene group or an alkylene group having 2 to 4 carbon atoms).
X-Examples of the halogen anion include a chloride ion, a bromide ion, and an iodide ion, and a chloride ion is preferable.
(4.1.1A Block)
In the step (a), the a block can be obtained by, for example, polymerizing a monomer composition containing a vinyl monomer having an acidic group.
The vinyl monomer having an acidic group used in the step (a) may be the above-mentioned vinyl monomer, and is preferably at least one selected from a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group. In addition, in the monomer composition for the a block, in addition to the vinyl monomer having an acidic group, a vinyl monomer which can form another structural unit of the a block may be mixed.
(4.1.2B Block)
In the step (a), the B block can be obtained by the following method: a method of polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the general formula (2) and a vinyl monomer capable of forming a structural unit represented by the general formula (3); a method in which a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the general formula (2) is polymerized, and a part of the tertiary amine structure of the structural unit represented by the general formula (2) in the obtained polymer is quaternized.
The vinyl monomer that can form the structural unit represented by the general formula (2) is not particularly limited, and examples thereof include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, and the like. The vinyl monomers which can form the structural unit represented by the general formula (2) may be used alone or in combination of two or more.
The vinyl monomer which can form the structural unit represented by the general formula (3) is not particularly limited, and examples thereof include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium chloride, (meth) acryloyloxybutyltrimethylammonium chloride, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxypropylbenzyldimethylammonium chloride, (meth) acryloyloxybutylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride, (meth) acryloyloxypropylbenzyldiethylammonium chloride, (meth) acryloyloxybutylbenzyldiethylammonium chloride; (meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxypropyltrimethylammonium bromide, (meth) acryloyloxybutyltrimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium bromide, (meth) acryloyloxypropylbenzyldimethylammonium bromide, (meth) acryloyloxybutylbenzyldimethylammonium bromide, (meth) acryloyloxyethylbenzyldiethylammonium bromide, (meth) acryloyloxypropylbenzyldiethylammonium bromide, (meth) acryloyloxybutylbenzyldiethylammonium bromide; (meth) acryloyloxyethyltrimethylammonium iodide, (meth) acryloyloxypropyltrimethylammonium iodide, (meth) acryloyloxybutyltrimethylammonium iodide, (meth) acryloyloxyethylbenzyldimethylammonium iodide, (meth) acryloyloxypropylbenzyldimethylammonium iodide, (meth) acryloyloxybutylbenzyldimethylammonium iodide, (meth) acryloyloxyethylbenzyldiethylammonium iodide, (meth) acryloyloxypropylbenzyldiethylammonium iodide, (meth) acryloyloxybutylbenzyldiethylammonium iodide; (meth) acryloyloxyethyltrimethylammonium fluoride, (meth) acryloyloxypropyltrimethylammonium fluoride, (meth) acryloyloxybutyltrimethylammonium fluoride, (meth) acryloyloxyethylbenzyldimethylammonium fluoride, (meth) acryloyloxypropylbenzyldimethylammonium fluoride, (meth) acryloyloxybutylbenzyldimethylammonium fluoride, (meth) acryloyloxyethylbenzyldiethylammonium fluoride, (meth) acryloyloxypropylbenzyldiethylammonium fluoride, (meth) acryloyloxybutylbenzyldiethylammonium fluoride and (meth) acryloyloxybutylbenzyldiethylammonium fluoride. The vinyl monomers which can form the structural unit represented by the general formula (3) may be used alone or in combination of two or more.
When the tertiary amine structure of the structural unit represented by the general formula (2) is quaternized, examples of the quaternizing agent include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; halogenated aralkyl such as benzyl chloride, benzyl bromide, benzyl iodide and the like. Among them, halogenated aralkyl such as benzyl chloride, benzyl bromide and benzyl iodide is preferable, and benzyl chloride is more preferable. The quaternized structure has an alkyl group or an aralkyl group introduced thereto from the quaternizing agent. Therefore, the amount of the structural unit represented by the general formula (3) can be estimated by measuring the amount of the alkyl group or aralkyl group introduced by the quaternization.
(4.1.3 method)
The step (a) may be performed by the following method: a method of preparing a block A and then polymerizing a monomer of a block B on the block A; a method of preparing a B block and then polymerizing a monomer of an A block on the B block; a method of coupling the A block and the B block after the A block and the B block are respectively manufactured; a method in which a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the general formula (2) is polymerized on an A block, and a part of the tertiary amine structure of the structural unit represented by the general formula (2) in the obtained polymer is quaternized; a method in which a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the general formula (2) is polymerized, a monomer of the A block is polymerized on the polymer, and a part of the tertiary amine structure of the structural unit represented by the general formula (2) in the obtained polymer is quaternized; a method comprising separately producing an A block and a block having a structural unit represented by the general formula (2), coupling these blocks, and then quaternarizing a part of the tertiary amine structure of the structural unit represented by the general formula (2) in the obtained polymer.
(4.1.4 living radical polymerization)
Although the polymerization method is not particularly limited, living radical polymerization is preferred. That is, as the first block copolymer, a copolymer obtained by polymerization using living radical polymerization is preferable. The conventional radical polymerization method causes not only initiation reaction and growth reaction but also termination reaction and chain transfer reaction to inactivate the growing end, and tends to form a mixture of polymers having various molecular weights and non-uniform compositions. The living radical polymerization method is preferable in terms of the ease of control of molecular weight distribution and the ease of production of a polymer having a uniform composition, because it is less likely to cause termination reaction and chain transfer, and enables growth without deactivation of the growing end, while maintaining the simplicity and versatility of conventional radical polymerization methods.
In the living radical polymerization method, the following methods are used depending on the method for stabilizing the polymerization growth end: a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); a method using an organotellurium compound (TERP method), and the like. Since the ATRP method uses an amine-based complex compound, the compound cannot be used unless the acid group of the vinyl monomer having an acid group is protected. When a plurality of monomers are used in the RAFT method, there are cases where it is difficult to form a low molecular weight distribution and there are problems such as a sulfur odor and coloring. Among these methods, the TERP method is preferably used from the viewpoint of the diversity of monomers that can be used, the molecular weight control in the polymer region, the composition uniformity, or the coloring.
The TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator, and is described in, for example, international publication No. 2004/14848, international publication No. 2004/14962, international publication No. 2004/072126, and international publication No. 2004/096870.
Specific polymerization methods of the TERP method include the following (a) to (d).
(a) A method for polymerizing a vinyl monomer using an organotellurium compound represented by the general formula (4).
(b) A method for polymerizing a vinyl monomer by using a mixture of an organic tellurium compound represented by the general formula (4) and an azo polymerization initiator.
(c) A method for polymerizing a vinyl monomer using a mixture of an organotellurium compound represented by the general formula (4) and an organoditellurium compound represented by the general formula (5).
(d) A method for polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (4), an azo polymerization initiator, and an organic ditellurium compound represented by the general formula (5).
Figure BDA0001659759100000231
(in the general formula (4), R41Represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. R42And R43Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R44Represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group. )
R41-Te-Te-R41 (5)
(in the general formula (5), R41Represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. )
R41The group is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, and is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Examples of the aryl group include phenyl and naphthyl.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
R42And R43The groups are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
R44The group is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group, and is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Examples of the aryl group include phenyl and naphthyl. Phenyl is preferred.
Examples of the substituted aryl group include a substituted phenyl group and a substituted naphthyl group. Examples of the substituent of the substituted aryl group include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group and-COR441The carbonyl-containing group (R) shown441Alkyl group having 1 to 8 carbon atoms, aryl group, alkoxy group or aryloxy group having 1 to 8 carbon atoms), sulfonyl group, trifluoromethyl group, etc. Further, these substituents are preferably substituted for one or two.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Amide group, there may be mentioned-CONR4421R4422(R4421、R4422Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
The oxycarbonyl group is preferably-COOR443(R443A hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group), and examples thereof include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butoxycarbonyl group, an sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-pentyloxycarbonyl group, and a phenoxycarbonyl group. Preferable oxycarbonyl group includes methoxycarbonyl group and ethoxycarbonyl group.
Allyl radical, there may be mentioned-CR4441R4442-CR4443＝CR4444R4445(R4441、R4442Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R4443、R4444、R4445Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and each substituent may be bonded to each other in a cyclic structure).
Propargyl, as exemplified by-CR4451R4452-C≡CR4453(R4451、R4452Is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R4453A hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or a silyl group).
Specific examples of the organic tellurium compound represented by the general formula (4) include (methyltelluromethyl) benzene, (methyltelluromethyl) naphthalene, ethyl-2-methyl-2-methyltelluro-propionate, ethyl-2-methyl-2-n-butyltelluro-propionate, (2-trimethylsilyloxyethyl) -2-methyl-2-methyltelluro-propionate, all of the organic tellurium compounds described in (2-hydroxyethyl) -2-methyl-2-methyltelluro-propionate or (3-trimethylsilylpropargyl) -2-methyl-2-methyltelluro-propionate, International publication No. 2004/14848, International publication No. 2004/14962, International publication No. 2004/072126 and International publication No. 2004/096870.
Specific examples of the organic ditelluride compound represented by the general formula (5) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di-n-butyl ditelluride, di-sec-butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyldelluride, diphenyl ditelluride, bis (p-methoxyphenyl) ditelluride, bis (p-aminophenyl) ditelluride, bis (p-nitrophenyl) ditelluride, bis (p-cyanophenyl) ditelluride, bis (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride and dipyridyl ditell.
The azo polymerization initiator is not particularly limited, and any azo polymerization initiator can be used as long as it is used in general radical polymerization. Examples thereof include 2, 2 '-azobis (isobutyronitrile) (AIBN), 2' -azobis (2-methylbutyronitrile) (AMBN), 2 '-azobis (2, 4-dimethylvaleronitrile) (ADVN), 1' -azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl 2, 2 '-azobisisobutyrate (MAIB), 4' -azobis (4-cyanovaleric acid) (ACVA), 1 '-azobis (1-acetoxy-1-phenylethane), 2' -azobis (2-methylbutyronide), 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile) (V-70), 2' -azobis (2-methylaminopropane) dihydrochloride, 2, 2 ' -azobis [2- (2-imidazolin-2-yl) propane ], 2 ' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2 ' -azobis (2, 4, 4-trimethylpentane), 2-cyano-2-propylazoformamide, 2 ' -azobis (N-butyl-2-methylpropionamide), 2 ' -azobis (N-cyclohexyl-2-methylpropionamide), and the like.
In the polymerization step, an azo polymerization initiator and/or an organic ditellurium compound represented by the general formula (5) are further mixed with the vinyl monomer and the organic tellurium compound represented by the general formula (4) depending on the type of the vinyl monomer in the vessel substituted with the inert gas for the purpose of promoting the reaction, controlling the molecular weight and the molecular weight distribution, and the like. In this case, examples of the inert gas include nitrogen, argon, helium and the like. Argon and nitrogen are preferred.
In the polymerization methods of (a), (b), (c) and (d), the amount of the vinyl monomer to be used may be appropriately adjusted depending on the physical properties of the objective copolymer, but it is generally preferable to set the vinyl monomer to 5 to 10000 moles per 1 mole of the organotellurium compound represented by the general formula (4).
In the polymerization method (b), when the organic tellurium compound represented by the general formula (4) and the azo polymerization initiator are used in combination, it is generally preferable that the azo polymerization initiator is used in an amount of 0.01 to 10 moles per 1 mole of the organic tellurium compound represented by the general formula (4).
In the polymerization method of the above (c), when the organotellurium compound represented by the general formula (4) and the organoditellurium compound represented by the general formula (5) are used in combination, it is generally preferable that the amount of the organoditellurium compound represented by the general formula (5) is 0.01 to 100 moles per 1 mole of the organoditellurium compound represented by the general formula (4) used.
In the polymerization method of the above (d), when the organic tellurium compound represented by the general formula (4), the organic ditellurium compound represented by the general formula (5) and the azo polymerization initiator are used in combination, it is generally preferable that the azo polymerization initiator is used in an amount of 0.01 to 100 moles per 1 mole of the total amount of the organic tellurium compound represented by the general formula (4) and the organic ditellurium compound represented by the general formula (5).
The polymerization reaction may be carried out without a solvent, but may be carried out by stirring the mixture using an aprotic solvent or a protic solvent which is generally used in radical polymerization. Examples of the aprotic solvent that can be used include benzene, toluene, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform, carbon tetrachloride, Tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, and trifluoromethylbenzene. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, and diacetone alcohol.
The amount of the solvent to be used may be appropriately adjusted, and is, for example, preferably 0.01ml or more, more preferably 0.05ml or more, further preferably 0.1ml or more, preferably 50ml or less, more preferably 10ml or less, and further preferably 1ml or less, based on 1g of the vinyl monomer.
The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained, but the reaction is usually carried out at 0 to 150 ℃ for 1 minute to 100 hours under stirring. The TERP process can achieve high yields and precise molecular weight distributions even at low polymerization temperatures and short polymerization times. At this time, the pressure is usually normal pressure, but may be increased or decreased.
After the polymerization reaction is completed, the target copolymer can be isolated by removing the solvent used, the residual vinyl monomer, and the like from the obtained reaction mixture by a usual separation and purification means.
The growing end of the copolymer obtained by polymerization is-Ter41(in the formula, R41The same as above), although the tellurium atom is continuously deactivated by the operation in the air after the completion of the polymerization reaction, it may remain. Since a copolymer having tellurium atoms remaining at the terminal ends is colored or has poor thermal stability, it is preferable to remove the tellurium atoms.
As a method for removing tellurium atoms, the following methods can be used: a radical reduction method using tributylstannane, a thiol compound, or the like; adsorption method using active carbon, silica gel, active alumina, active white clay, molecular sieve and high molecular adsorbent; a method of adsorbing a metal with an ion exchange resin or the like; a liquid-liquid extraction method or a solid-liquid extraction method in which a peroxide such as hydrogen peroxide or benzoyl peroxide is added or air or oxygen is blown into the system to oxidatively decompose tellurium atoms at the terminal of the copolymer, and the residual tellurium compound is removed by water washing or a suitable solvent; a method of purification in the state of a solution such as ultrafiltration, in which only substances having a molecular weight of not more than a specific molecular weight are extracted and removed. Further, these methods may be used in combination.
(4.1.5 Quaternary ammonium)
A method for quaternizing a part of the tertiary amine structure of the structural unit represented by the general formula (2) in the polymer includes a method of contacting the polymer with a quaternizing agent. Specifically, a method in which a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the general formula (2) is polymerized, and then a quaternizing agent is added to the reaction solution and stirred can be exemplified.
The temperature of the reaction solution to which the quaternizing agent is added is preferably 55 to 65 ℃ and the stirring time is preferably 5 to 20 hours. When the quaternizing agent is added, it is also preferable to dilute the reaction solution after the polymerization. The solvent to be added for dilution is a solvent usable for polymerization, preferably a protic solvent, and more preferably methanol.
(4.1.6 precursors of Block copolymers)
The molecular weight of the precursor of the block copolymer was measured by a GPC method. The weight average molecular weight (Mw) of the precursor of the block copolymer is preferably 5000 or more, more preferably 6000 or more, further preferably 7000 or more, preferably 15000 or less, more preferably 12000 or less, further preferably 10000 or less.
The molecular weight distribution (PDI) of the precursor of the block copolymer is preferably 2.0 or less, more preferably 1.6 or less.
The content of the a block in the precursor of the block copolymer is preferably 35% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less, based on 100% by mass of the entire block copolymer. The content of the B block in the precursor of the block copolymer is preferably 15 mass% or more, more preferably 20 mass% or more, further preferably 25 mass% or more, preferably 65 mass% or less, more preferably 60 mass% or less, and further preferably 55 mass% or less, based on 100 mass% of the entire block copolymer.
From the viewpoint of pigment adsorption and pigment dispersibility, the amine value of the precursor of the block copolymer is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, further preferably 30mgKOH/g or more, preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, further preferably 100mgKOH/g or less. The amine value of the precursor of the block copolymer is derived from a structural unit represented by the general formula (2).
The acid value of the precursor of the block copolymer is preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, further preferably 15mgKOH/g or more, preferably 50mgKOH/g or less, more preferably 40mgKOH/g or less, further preferably 35mgKOH/g or less.
(4.2 Process (B))
In the step (B), after the step (a) is completed, an alkali metal salt of at least one selected from the group consisting of aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid is allowed to act on a precursor of the obtained block copolymer to obtain a block copolymer. In the step (B), the halogen anion contained in the structural unit represented by the general formula (3) can be exchanged (anion exchange) with an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonium ion or an aromatic carboxylic acid anion.
The alkali metal in the alkali metal salt of at least one selected from the group consisting of aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid, and aromatic carboxylic acid is lithium, sodium, potassium, rubidium, cesium, and francium, and among them, lithium, sodium, and potassium are preferable from the viewpoint of economic advantage.
Examples of the alkali metal salt of the aromatic dicarboxylic acid imide include salts represented by the general formula (6).
Figure BDA0001659759100000281
(in the general formula (6), the ring A represents an optionally substituted aromatic ring, and M1Represents an alkali metal. )
In the general formula (6), the aromatic ring constituting the ring A means a ring structure having aromatic properties. The aromatic ring includes any of monocyclic rings and fused rings. The monocyclic ring is preferably a five-or six-membered ring, suitably a benzene ring, furan ring, thiophene ring, pyrrole ring. The condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, a halogen group, and the like. M1Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium.
Examples of the alkali metal salt of the aromatic dicarboxylic acid imide include salts represented by the general formulae (6-1) to (6-7).
Figure BDA0001659759100000291
(in the general formulae (6-1) to (6-7), M1Represents an alkali metal. )
Examples of the alkali metal salt of the aromatic sulfonic acid include salts represented by the general formula (7).
Figure BDA0001659759100000292
(in the general formula (7), Ar represents an optionally substituted aromatic ring, M2Represents an alkali metal. )
In the general formula (7), the aromatic ring constituting Ar means a ring structure having aromatic properties. The aromatic ring includes any of monocyclic rings and fused rings. The monocyclic ring is preferably a five-or six-membered ring, suitably a benzene ring, furan ring, thiophene ring, pyrrole ring. The condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, a halogen group, and the like. M2Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium.
Examples of the alkali metal salt of the aromatic sulfonic acid include salts represented by the general formulae (7-1) to (7-9).
Figure BDA0001659759100000301
(in the general formulae (7-1) to (7-9), M2Represents an alkali metal. )
The alkali metal salt of an aromatic phosphonic acid includes, for example, a salt represented by the general formula (8).
Figure BDA0001659759100000302
(in the general formula (8), Ar represents an optionally substituted aromatic ring, M3Represents an alkali metal. )
In the general formula (8), the aromatic ring constituting Ar isRefers to a ring structure having aromatic character. The aromatic ring includes any of monocyclic rings and fused rings. The monocyclic ring is preferably a five-or six-membered ring, suitably a benzene ring, furan ring, thiophene ring, pyrrole ring. The condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, a halogen group, and the like. M3Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium.
Examples of the alkali metal salt of the aromatic phosphonic acid include salts represented by the general formulae (8-1) to (8-7).
Figure BDA0001659759100000311
(in the general formulae (8-1) to (8-7), M3Represents an alkali metal. )
Examples of the alkali metal salt of the aromatic carboxylic acid include salts represented by the general formula (9).
Figure BDA0001659759100000312
(in the general formula (9), Ar represents an optionally substituted aromatic ring, M4Represents an alkali metal. )
In the general formula (9), the aromatic ring constituting Ar means a ring structure having aromaticity. The aromatic ring includes any of monocyclic rings and fused rings. The monocyclic ring is preferably a five-or six-membered ring, suitably a benzene ring, furan ring, thiophene ring, pyrrole ring. The condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, a halogen group, and the like. M4Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and francium.
Examples of the alkali metal salt of the aromatic carboxylic acid include salts represented by the general formulae (9-1) to (9-9).
Figure BDA0001659759100000321
In the step (B), the alkali metal salt is allowed to act on the precursor of the block copolymer, and a method of adding the alkali metal salt to a solution in which the precursor of the block copolymer is dissolved and stirring the solution can be mentioned.
In the step (B), the alkali metal salt may be added to the reaction solution after the polymerization in the step (a). From the viewpoint of anion exchange efficiency, it is preferable to separate a precursor of the block copolymer from the polymerization solution after completion of the step (a), dissolve the precursor in a new solvent, and add the alkali metal salt to the obtained solution.
As the solvent capable of dissolving the precursor of the block copolymer, an aprotic solvent or a protic solvent can be used. Examples of the aprotic solvent that can be used include benzene, toluene, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform, carbon tetrachloride, Tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, and trifluoromethylbenzene. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, and diacetone alcohol.
In the step (B), the amount of the solvent used for dissolving the precursor of the block copolymer can be suitably adjusted, and is, for example, usually in the range of 2ml to 10ml, preferably 2ml to 5ml, based on 1g of the precursor of the block copolymer.
In step (B), the amount of the alkali metal salt of at least one member selected from the group consisting of aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid, and aromatic carboxylic acid is preferably 0.5 equivalents or more, more preferably 0.9 equivalents or more, preferably 1.1 equivalents or less, and more preferably 1.0 equivalent or less, based on the quaternary ammonium group.
In the step (B), the solution temperature at the time of contacting the precursor of the block copolymer with the alkali metal salt is usually 55 to 70 ℃ and preferably 55 to 65 ℃, and the stirring time is usually 18 to 24 hours and preferably 20 to 22 hours.
After the reaction is completed, the solvent is removed from the reaction solution to obtain a first composition containing a block copolymer. It is preferable to remove impurities such as a salt (a salt formed from a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide) precipitated from the obtained first composition by filtration.
(4.3 Process (C))
The method for producing a block copolymer preferably includes a step (C) of washing the block copolymer obtained in the step (B) with water. The washing method may be a known washing method, but liquid separation washing is preferable. The liquid separation washing may be performed with respect to the solution after the completion of the step (B), or may be performed with respect to the following solutions: a solution obtained by separating the first composition of the block copolymer from the solution after the completion of the step (B) and dissolving the obtained first composition in a suitable solvent.
As a specific example of the above-mentioned liquid-separation washing, a solvent in which the block copolymer is dissolved is mixed with water, and then the separated water layer is removed. The content of a salt (a salt formed by a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide) contained in the first composition can be further reduced by washing with water. Further, by further repeating the liquid-separation washing, a better effect can be obtained. After the liquid separation and washing, the solvent in which the phase of the block copolymer is dissolved is removed under reduced pressure, whereby a second composition of the target block copolymer can be obtained.
The solvent used in the above-mentioned liquid separation operation may be any solvent which can dissolve the block copolymer and can be phase-separated from water, and examples thereof include ethyl acetate, butyl acetate, isopropyl acetate, and methyl isobutyl ketone. These solvents may also be used in combination. Further, the water used for the water washing may also contain an alcohol or the like.
In the above-mentioned liquid-separation washing, the amount of water used is preferably 0.1 to 10 times, and more preferably 0.5 to 5 times, by volume ratio, the amount of the solvent phase in which the block copolymer is dissolved. The liquid temperature at the time of the liquid separation washing is preferably 10 to 60 ℃, more preferably 30 to 50 ℃, and particularly preferably 35 to 45 ℃.
<5 dispersing agent, pigment Dispersion composition >
The dispersant of the present invention contains the above-mentioned block copolymer, first composition or second composition as a main component. The dispersant is preferably substantially composed only of the block copolymer, the first composition or the second composition of the present invention. The pigment-dispersion composition of the present invention contains the dispersant, the pigment and the dispersion solvent. The kind and particle size of the pigment used in this case are not particularly limited, and vary depending on the application. The pigment-dispersion composition is useful for color filters. The block copolymer of the present invention is considered to exert an effect of improving the dispersibility of the pigment by strongly bonding the tertiary amine group and quaternary ammonium salt group (B block) in the structure thereof to the acid group of the acid pigment or the pigment treated with the acid group-containing pigment derivative and adsorbing the B block to the pigment, or by adsorbing the aromatic site of the aromatic dicarboxylic acid imide anion which is a counter ion of the quaternary ammonium salt group to the pigment skeleton site of the pigment. That is, the dispersant of the present invention is a component that well disperses the pigment by this action, and therefore the kind of the dispersed pigment is not particularly limited.
In the pigment-dispersion composition, the content of the dispersant is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and still more preferably 10 to 50 parts by mass, based on 100 parts by mass of the pigment.
The pigment may be any of an organic pigment and an inorganic pigment, but an organic pigment containing an organic compound as a main component is particularly preferable. Examples of the pigment include pigments of various colors such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a violet pigment. Examples of the structure of the pigment include azo pigments such as monoazo pigments, diazo pigments, and condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. The pigment contained in the pigment-dispersion composition may be only one kind or may be plural kinds.
Specific examples of the pigment include c.i. pigment Red (c.i. pigment Red)7, 9, 14, 41, 48: 1. 48: 2. 48: 3. 48: 4. 81: 1. 81: 2. 81: 3. 122, 123, 146, 149, 168, 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264 and the like; yellow pigments such as c.i. pigment Yellow (c.i. pigment Yellow)1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, 150, 151, 154, 155, 166, 167, 168, 170, 180, 188, 193, 194, 213, and the like; orange pigments such as c.i. pigment Orange 36, 38, 43; c.i. pigment Blue (c.i. pigment Blue)15, 15: 2. 15: 3. 15: 4. 15: 6. 16, 22, 60, and the like; green pigments such as c.i. pigment Green 7, 36, and 58; violet pigments such as c.i. pigment Violet (c.i. pigment Violet)23, 32, 50, and the like. The pigment is preferably c.i. pigment red 254, c.i. pigment red 255, c.i. pigment red 264, c.i. pigment blue 15: 2. c.i. pigment blue 15: 3. c.i. pigment blue 15: 4. c.i. pigment blue 15: 6. c.i. pigment blue 16, c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 58, and the like.
The upper limit of the pigment content in the pigment-dispersion composition is usually 80% by mass, preferably 70% by mass, and more preferably 60% by mass, of the total solid content of the pigment-dispersion composition. The lower limit of the pigment content in the pigment-dispersion composition is usually 10 mass%, preferably 20 mass%, and more preferably 30 mass% of the total solid content of the pigment-dispersion composition.
Examples of the dispersion solvent include conventionally known organic solvents, and examples thereof include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl amyl alcohol, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxyamyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; glycol diacetate esters such as ethylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl pentanone, methyl isopropyl ketone, diisopropyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentanone, methyl butanone, methyl hexanone, methyl nonanone, and methoxymethyl pentanone; monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerol, and benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; chain or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and pentyl chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile. The organic solvent is preferably a glycol alkyl ether acetate, a monohydric or polyhydric alcohol, from the viewpoints of dispersibility of the pigment or the like, solubility of the dispersant, coatability of the pigment dispersion composition, and the like. The solvent contained in the pigment-dispersion composition may be only one kind or may be plural kinds.
The content of the dispersion solvent in the pigment-dispersion composition is not particularly limited and may be appropriately adjusted. The upper limit of the content of the dispersion solvent in the pigment-dispersion composition is usually 99% by mass. Further, the lower limit value of the content of the dispersion solvent in the pigment-dispersion composition is usually 70% by mass, preferably 80% by mass, in view of the viscosity suitable for coating the pigment-dispersion composition. The above-mentioned dispersion solvent can be used as a solvent for dissolving and removing precipitates formed from the pigment-dispersion composition.
The pigment-dispersion composition of the present invention preferably further contains an acidic pigment derivative having an acidic group for the purpose of ionic bonding with and adsorption to the tertiary amine group and quaternary ammonium salt group in the block copolymer of the present invention used for the dispersant. The dye derivative is a substance having an acidic functional group introduced into a dye skeleton. The pigment skeleton is preferably the same as or similar to the pigment constituting the pigment dispersion composition, or the same as or similar to the compound as the raw material of the pigment. Specific examples of the pigment skeleton include azo-based pigment skeleton, phthalocyanine-based pigment skeleton, anthraquinone-based pigment skeleton, triazine-based pigment skeleton, acridine-based pigment skeleton, perylene-based pigment skeleton, and the like. The acidic group introduced into the dye skeleton is preferably a carboxyl group, a phosphate group, or a sulfonate group. In view of ease of synthesis and the strength of acidity, a sulfonic acid group is preferable. The acidic group may be bonded directly to the pigment skeleton, but may be bonded to the pigment skeleton via a hydrocarbon group such as an alkyl group or an aryl group, an ester group, an ether group, a sulfonamide group, or a urethane bond.
The pigment-dispersion composition of the present invention may further contain a binder resin. The binder resin may also be a polymer, for example. When the binder resin is a polymer, specific examples of monomers constituting the polymer include carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, and maleic anhydride; (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and cyclododecyl (meth) acrylate; and aromatic unsaturated monomers (styrene-based monomers) such as styrene, α -methylstyrene, 4-methylstyrene (p-methylstyrene), 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methoxystyrene (p-methoxystyrene), p-tert-butylstyrene, p-n-butylstyrene, and p-tert-butylstyrene.
When the pigment dispersion composition is used as a colorant for color filters, the binder resin is preferably a copolymer of a carboxyl group-containing unsaturated monomer and a (meth) acrylate. Specific examples of such a copolymer include a copolymer of (meth) acrylic acid and butyl (meth) acrylate, a copolymer of (meth) acrylic acid and benzyl (meth) acrylate, and a copolymer of (meth) acrylic acid and butyl (meth) acrylate and benzyl (meth) acrylate. The binder resin is particularly preferably a copolymer of (meth) acrylic acid and benzyl (meth) acrylate from the viewpoint of affinity of the binder resin with the pigment. In the copolymer of a carboxyl group-containing unsaturated monomer and a (meth) acrylic acid ester, the content of (meth) acrylic acid in the total monomer components is usually 5 to 90% by mass, preferably 10 to 70% by mass, and more preferably 20 to 70% by mass. The Mw is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the heat resistance, film strength and the like of a coating film formed from the pigment dispersion composition become better, and when the Mw is 100,000 or less, the developability of the coating film using an alkaline aqueous solution becomes better.
When the pigment dispersion composition is used as a colorant for color filters, the acid value of the binder resin is preferably from 20mgKOH/g to 170mgKOH/g, more preferably from 50mgKOH/g to 150mgKOH/g, and still more preferably from 90mgKOH/g to 150 mgKOH/g. When the acid value of the binder resin is 20mgKOH/g or more, the alkali developability in the case of forming the pigment dispersion composition into a coating film is more preferable, and when it is 170mgKOH/g or less, the heat resistance is more preferable.
The binder resin contained in the pigment-dispersion composition may be only one kind or may be plural kinds. The content of the binder resin in the pigment-dispersion composition is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and still more preferably 10 to 50 parts by mass, based on 100 parts by mass of the pigment.
The pigment dispersion composition can be obtained by mixing a pigment, a dispersant, a dispersion solvent, a pigment derivative, a binder resin, and the like using a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, and a kneader, for example. The pigment-dispersion composition is preferably filtered after mixing.
The pigment-dispersion composition may contain other additives as necessary. Examples of the other additives include photopolymerizable monomers, photopolymerization initiators, pH adjusters, antioxidants, ultraviolet absorbers, light stabilizers, preservatives, and mildewcides. The photopolymerizable monomer is preferably a compound having at least two ethylenically unsaturated double bonds, which is compatible with the binder resin, or the like. When the pigment-dispersion composition is used as a colorant for color filters, such a compound is preferably a compound having an alkali solubility and having one or more acid groups and two or more ethylenically unsaturated bonds in one molecule, and more preferably a compound having one or more acid groups and three or more ethylenically unsaturated bonds in one molecule. Examples of the compound having at least two ethylenically unsaturated double bonds include polyfunctional (meth) acrylates such as bifunctional (meth) acrylates and trifunctional or higher (meth) acrylates. Among them, trifunctional or higher (meth) acrylates are preferable. The compound having one or more acidic groups and two or more ethylenically unsaturated bonds in one molecule is more preferably an acidic group-containing polyfunctional (meth) acrylate, and particularly preferably a trifunctional or higher acidic group-containing polyfunctional (meth) acrylate. The acidic group may be any group that can be developed with an alkali, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acidic group is preferably a carboxyl group from the viewpoint of further improving the alkali developability and the handling property of the resin composition.
The pigment-dispersion composition can be applied to a substrate by a method such as a spin coating method, a roll coating method, or a slit coating method, thereby forming a coating film of the pigment-dispersion composition on the substrate. After the pigment-dispersion composition is applied to the substrate, drying (desolvation treatment) or the like may be performed as necessary.
When the pigment-dispersion composition of the present invention is used as, for example, a pattern-forming material for a color filter, since the block copolymer of the present invention used as a dispersant is excellent in heat resistance, it is expected that a decrease in contrast, a change in chromaticity, and the like before and after a high-temperature process will be suppressed.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these specific examples. Further, various physical properties were measured by the following instruments. The meanings of the abbreviations are as follows.
BTEE: ethyl-2-methyl-2-n-butyl tellurium-propionate
DBDT: dibutyl ditelluride
AIBN: 2, 2' -azobis (isobutyronitrile)
MMA: methacrylic acid methyl ester
BMA: methacrylic acid butyl ester
EHMA: 2-ethylhexyl methacrylate
BzMA: methacrylic acid benzyl ester
M4 EGM: methoxypolyethylene glycol monomethacrylate (trade name: ブレンマー PME-200, manufactured by Nichii oil Co., Ltd.)
HEMA: 2-hydroxyethyl methacrylate
THFMA: methacrylic acid tetrahydrofuran ester
PCL 5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daiiol chemical Co., Ltd., プラクセル (registered trademark) FM5)
MAA: methacrylic acid
DMAEMA: dimethylaminoethyl methacrylate
BzCl: benzyl chloride
PIK: phthalimide potassium salt
NaSS: sodium p-styrene sulfonate
NaTS: sodium p-toluenesulfonate
NaBA: sodium benzoate
NaHPPA: phenylphosphonic acid monosodium salt
PMA: propylene glycol monomethyl ether acetate
MP: 1-methoxy-2-propanol
AcOEt: ethyl acetate
(polymerization ratio)
Measurement was carried out using a Nuclear Magnetic Resonance (NMR) measuring apparatus (model: AVANCE500 (frequency 500MHz), manufactured by Bruker, Germany)1H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane). From the obtained NMR spectrum, the integral ratio of the peak derived from the vinyl group of the monomer to the peak derived from the ester side chain of the polymer was obtained, and the polymerization rate of the monomer was calculated.
(weight average molecular weight (Mw) and molecular weight distribution (PDI))
The measurement was carried out by Gel Permeation Chromatography (GPC) using a high performance liquid chromatograph (model: HLC8320, manufactured by Tosoh corporation). The column used was a SHODEX KF-603 (. PHI.6.0 mm. times.150 mm) (manufactured by SHODEX K.K.), the mobile phase used 30 mmol/L lithium bromide-30 mmol/L acetic acid-N-methylpyrrolidone, and the detector used a differential refractive index detector. The measurement conditions were: the column temperature was 40 ℃, the sample concentration was 100mg/mL, the sample injection amount was 10. mu.L, and the flow rate was 0.6 mL/min. A calibration curve (calibration curve) was prepared using polystyrene (TSK standard, manufactured by tokyo corporation) as a standard substance, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured. From these measurements, the molecular weight distribution (PDI) was calculated.
(amine number)
The amine value is a value expressed by the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of the solid component. The measurement sample was dissolved in tetrahydrofuran, and the resulting solution was neutralized and titrated with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potentiometric titrator (trade name: 915KF Ti-touch, manufactured by Vantone, Switzerland). The inflection point of the titration pH curve was used as the titration end point, and the amine value (B) was calculated according to the following formula.
B＝56.11×Vs×0.1×f/w
B: amine number (mgKOH/g)
Vs: the amount of 0.1 mole/L hydrochloric acid/2-propanol solution required for titration (mL)
f: titrimetry of 0.1 mol/L hydrochloric acid/2-propanol solution
w: measurement of sample Mass (g) (solid content conversion value)
(acid value)
The acid value is a value representing the mass of potassium hydroxide required for neutralizing the acidic component per gram of the solid component. The measurement sample was dissolved in tetrahydrofuran, and the resulting solution was neutralized and titrated with a 0.5 mol/L potassium hydroxide/ethanol solution. The acid value (A) was calculated according to the following formula.
A＝56.11×Vs×0.5×f/w
A: acid value (mgKOH/g)
Vs: the amount of 0.5 mol/L KOH/ethanol solution (mL) required for titration
f: titre of 0.5 mol/L KOH/ethanol solution
w: measurement of sample Mass (g) (solid content conversion value)
(viscosity)
The viscosity was measured at 25 ℃ at a spindle rotation speed of 100rpm using an E-type viscometer (trade name: TVE-22L, manufactured by Toyobo Co., Ltd.) and a conical rotor (1 ℃ C. times.34'. times.R 24).
(temperature for reducing weight by heating)
Measurement was performed using a thermogravimetry-differential heat simultaneous measurement apparatus (TG-DTA) (TG-DTA 6300, manufactured by Seiko nanotechnology Inc.). The samples were dried under reduced pressure at 130 ℃ for 2 hours before measurement. The measurement conditions were: the sample mass was about 10mg, the air inflow was 200 ml/min, the temperature rise rate was 10 ℃/min, and the measurement temperature range was 40 ℃ to 600 ℃. The temperature at which the mass of the sample decreased by 10% was read from the obtained TG curve, and this temperature was defined as the heating weight reduction temperature.
(content of halogen anion)
Sample preparation was performed as follows. About 10mg of the second composition was charged into a combustion furnace (trade name: AQF-2100H, manufactured by Mitsubishi chemical analysis technology Co., Ltd.). The heater of the furnace was set at 900 ℃ (inside), the gas flow rates were set at 200 mL/min argon, 400 mL/min oxygen, 100 mL/min argon for humidification, and the furnace residence time was set at 15 minutes. The exhaust gas was trapped by a trap (trade name: AU-250, manufactured by Mitsubishi chemical analysis Co., Ltd.). Using ultrapure water as the absorbing solution, 35mL of the obtained absorbing solution was diluted to 50mL with ultrapure water to prepare a sample solution.
The content of halogen anion was measured by using an ion chromatograph (trade name: DIONEX ICS-1600, manufactured by Saimer Feishol science, USA). Ion Pac AS-14A (manufactured by Daian, USA) was used AS a column, and an anion analysis eluent (trade name: AS12A, manufactured by Daian, USA) was used AS an eluent. The measurement conditions were: the sample was injected in an amount of 25. mu.L at a flow rate of 1.5 mL/min. A calibration curve (calibration curve) was prepared using a standard solution having a chloride anion concentration of 1ppm and 2ppm as a standard substance, and the chloride anion concentration was calculated.
< production of copolymer >
(precursor No.1 of Block copolymer)
A flask equipped with an argon gas line and a stirrer was charged with 46.1g of MMA, 22.2g of BMA, 20.9g of EHMA, 15.4g of BzMA, 8.1g of M4EGM, 8.1g of MAA, 0.82g of AIBN and 80.5g of PMA, and after replacement with argon gas, 7.49g of BTEE and 4.61g of DBDT were added to react at 60 ℃ for 15 hours to polymerize an A block. The polymerization rate was 99%.
A mixed solution of 54.3g of DMAEMA, 0.41g of AIBN and 36.2g of PMA, which had been previously substituted with argon, was added to the reaction solution, and the mixture was reacted at 60 ℃ for 10 hours to polymerize the B block. The polymerization rate was 98%.
After completion of the reaction, methanol (165g) previously substituted with argon was added to the reaction mixture to dilute the mixture, and benzyl chloride (15.3g) was added to the diluted mixture to carry out a reaction at 60 ℃ for 10 hours to effect quaternization.
After the reaction was completed, the reaction mixture was poured into n-heptane with stirring. The precipitated polymer was subjected to suction filtration and dried to obtain a precursor No.1 of a block copolymer. The precursor No.1 of the obtained block copolymer had Mw of 7618, PDI of 1.30, an acid value of 32mgKOH/g, an amine value of 64mgKOH/g, and a heating weight-loss temperature of 254 ℃.
(Block copolymer precursor No.2 to 12)
Precursors No.2 to 12 of block copolymers were prepared in the same manner as the preparation method of the precursor No.1 of block copolymer. The raw material monomers, organotellurium compounds, organoditellurium compounds, azo polymerization initiators, solvents, quaternizing agents, reaction conditions and polymerization ratios used are shown in tables 1 and 2. The composition, Mw, PDI, acid value, amine value, and heating weight reduction temperature of the precursor of each block copolymer are shown in tables 3 and 4.
[ Table 1]
Figure BDA0001659759100000421
[ Table 2]
Figure BDA0001659759100000431
[ Table 3]
Figure BDA0001659759100000441
[ Table 4]
Figure BDA0001659759100000442
(first composition No.31 of Block copolymer)
110g of PMA and 110g of MP were added to 187.5 g of the block copolymer precursor obtained above, and dissolved. To the resulting solution was added 11.2g of PIK, and the mixture was reacted at 60 ℃ for 20 hours to effect anion exchange. After the reaction solution was filtered, the solvent was removed from the filtrate to obtain first composition No.31 of a block copolymer. The block copolymer contained in the first composition No.31 thus obtained had Mw of 7479 and PDI of 1.23, the acid value of the first composition No.31 was 31mgKOH/g, the amine value was 101mgKOH/g, and the temperature for weight reduction by heating was 273 ℃.
(first composition No.32 to 46 of Block copolymer)
First composition Nos. 32 to 46 were produced in the same manner as in the production method of first composition No.31 of the block copolymer. The raw material copolymer, anion exchanger, solvent and reaction conditions used are shown in tables 5 and 6. Further, the composition, Mw, PDI, and acid value, amine value, and heating weight reduction temperature of the block copolymer contained in the first composition are shown in tables 7 and 8.
[ Table 5]
Figure BDA0001659759100000451
[ Table 6]
Figure BDA0001659759100000452
[ Table 7]
Figure BDA0001659759100000461
[ Table 8]
Figure BDA0001659759100000471
(second composition No.51 of Block copolymer)
110g of PMA and 110g of MP were added to 187.5 g of the block copolymer precursor obtained above, and dissolved. To the resulting solution was added 11.2g of PIK, and the mixture was reacted at 60 ℃ for 20 hours to effect anion exchange. The obtained reaction solution was cooled, and then ethyl acetate and water were added thereto, followed by stirring at 40 ℃ for 1 hour. The organic layer was obtained by liquid separation. The obtained organic layer was concentrated under reduced pressure and dried to obtain second composition No.51 of a block copolymer. The Mw of the block copolymer contained in the second composition No.51 of the block copolymer obtained was 7852 and the PDI was 1.21. The acid value of the second composition was 32mgKOH/g, the amine value was 89mgKOH/g, the temperature for weight loss by heating was 291 ℃ and the chloride anion content was 3501ppm (calculated amount on solid content).
(second composition No.52 to 65 of Block copolymer)
Second compositions Nos. 53 to 65 were prepared in the same manner as the preparation method of the second composition No.51 of the block copolymer. The composition, Mw, PDI, and acid value, amine value, and heating weight reduction temperature of the block copolymer contained in the second composition are shown in tables 9 and 10. The obtained second composition No.59 had a chlorine anion content of 6615ppm (in terms of solid content).
[ Table 9]
Figure BDA0001659759100000481
[ Table 10]
Figure BDA0001659759100000482
< production of pigment Dispersion composition >
(pigment Dispersion composition 1)
A pigment dispersion composition was prepared in a ratio of c.i. pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals Inc.) 10 parts by mass, a precursor of a block copolymer No. 13 parts by mass, a binder resin (a resin polymerized at a mass ratio of benzyl methacrylate/methacrylic acid of 80/20, Mw 12024, PDI 1.83, an acid value of 130mgKOH/g, a PMA solution having a solid content of 39 mass%), MP 3 parts by mass, and PMA 81 parts by mass, and stirred for 2 hours with a planetary ball mill (0.3mm zirconia beads). The viscosity of the obtained pigment-dispersion composition was 4.0 mPas.
(pigment Dispersion composition 2)
A pigment dispersion composition was prepared by mixing 10 parts by mass of c.i. pigment Red 254 (trade name: BKCF, manufactured by gasoline refiner), 513 parts by mass of a second composition of a block copolymer, 3 parts by mass of a binder resin (a PMA solution having a mass ratio of benzyl methacrylate/methacrylic acid of 80/20, Mw of 12024, PDI of 1.83, an acid value of 130mgKOH/g, and a solid content of 39%), 3 parts by mass of MP 3, and 81 parts by mass of PMA, and stirring the resulting mixture for 2 hours using a planetary ball mill (0.3mm zirconia beads). The viscosity of the obtained pigment-dispersion composition was 3.0 mPas.
The present invention includes the following embodiments.
(embodiment mode 1)
A block copolymer comprising an A block containing a structural unit derived from a vinyl monomer having an acidic group and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
Figure BDA0001659759100000491
(in the formula (1), R11、R12And R13Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R11、R12And R13Two or more of them may bond to each other and form a cyclic structure. X1Represents a divalent linking group. R14Represents a hydrogen atom or a methyl group. Y is-Is selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anionsAt least one member of the group. )
Figure BDA0001659759100000501
(in the formula (2), R21And R22Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R21And R22May bond to each other and form a cyclic structure. X2Represents a divalent linking group. R23Represents a hydrogen atom or a methyl group. )
(embodiment mode 2)
The block copolymer according to embodiment 1, which is an a-B type block copolymer.
(embodiment mode 3)
The block copolymer according to embodiment 1 or 2, wherein a content of the structural unit derived from the vinyl monomer having an acidic group in 100% by mass of the a block is 2% by mass to 20% by mass.
(embodiment mode 4)
The block copolymer according to any one of embodiments 1 to 3, wherein a content of the structural unit represented by the general formula (1) in 100% by mass of the B block is 30% by mass to 85% by mass.
(embodiment 5)
The block copolymer according to any one of embodiments 1 to 4, wherein a content of the A block in 100% by mass of the block copolymer is 35% by mass to 85% by mass.
(embodiment mode 6)
A first composition comprising the block copolymer according to any one of embodiments 1 to 5.
(embodiment 7)
The first composition of embodiment 6, wherein the molecular weight distribution PDI of the block copolymer is 2.0 or less.
(embodiment mode 8)
A second composition obtained by washing and drying the first composition described in embodiment 7.
(embodiment mode 9)
A dispersant comprising the block copolymer according to any one of embodiments 1 to 6, the first composition according to embodiment 7, or the second composition according to embodiment 8.
(embodiment mode 10)
A pigment-dispersion composition comprising the dispersant of embodiment 9, a pigment, and a dispersion solvent.
(embodiment mode 11)
The pigment-dispersion composition according to embodiment 10, which is used for a color filter.
(embodiment mode 12)
A method for producing a block copolymer, comprising the steps of:
a step (A) for preparing a precursor of a block copolymer, wherein the precursor of the block copolymer has an A block and a B block, the A block contains a structural unit derived from a vinyl monomer having an acidic group, and the B block contains a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (3); and (B) a step of obtaining a block copolymer by allowing an alkali metal salt of at least one member selected from the group consisting of aromatic dicarboxylic acid imides, aromatic sulfonic acids, aromatic phosphonic acids, and aromatic carboxylic acids to act on the precursor of the block copolymer obtained in the step (a).
Figure BDA0001659759100000511
(in the formula (2), R21And R22Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R21And R22May bond to each other and form a cyclic structure. X2Represents a divalent linking group. R23Represents a hydrogen atom or a methyl group. )
Figure BDA0001659759100000512
(in the formula (3), R31、R32And R33Each independently represents a chain or cyclic hydrocarbon group which may have a substituent. R31、R32And R33Two or more of them may bond to each other and form a cyclic structure. X3Represents a divalent linking group. R34Represents a hydrogen atom or a methyl group. X-Represents a halogen anion. )
(embodiment mode 13)
The method for producing a block copolymer according to embodiment 12, wherein in the step (a), a precursor of the first block copolymer is prepared by living radical polymerization.
(embodiment mode 14)
The method for producing a block copolymer according to embodiment 12 or 13, further comprising a step (C) of washing the block copolymer obtained in the step (B) with water.
Possibility of industrial utilization
The block copolymer of the present invention can be easily developed with an alkali due to the acidic group of the A block. Further, the counter ion of the quaternary ammonium cation in the B block is an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, or an aromatic carboxylic acid anion, and therefore, the heat resistance is excellent. Therefore, the block copolymer of the present invention is preferably used for a pigment dispersion composition for a color filter used for producing a color filter using alkali development.

Claims (14)

1. A block copolymer comprising an A block containing a structural unit derived from a vinyl monomer having an acidic group and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2):
Figure FDA0002708832820000011
in the formula (1), R11、R12And R13Each independently may have an accessLinear or cyclic hydrocarbyl radicals of radicals R11、R12And R13Two or more of them may bond with each other and form a cyclic structure; x1Represents a divalent linking group; r14Represents a hydrogen atom or a methyl group; y is-Represents at least one selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions,
Figure FDA0002708832820000012
in the formula (2), R21And R22Each independently represents a chain or ring-like hydrocarbon group which may have a substituent, R21And R22Can bond with each other and form a cyclic structure; x2Represents a divalent linking group; r23Represents a hydrogen atom or a methyl group,
in the general formula (1) described above,
Y-the aromatic dicarboxylic acid imide anion represented by (a) is at least one selected from the group consisting of anions represented by the following formulae (12-1) to (12-7):
Figure FDA0002708832820000021
Y-the aromatic sulfonic acid anion represented by (a) is at least one selected from the group consisting of anions represented by the following formulae (13-1) to (13-9):
Figure FDA0002708832820000022
Y-the aromatic phosphonic acid anion represented is at least one selected from the group consisting of anions represented by the following formulae (14-1) to (14-7):
Figure FDA0002708832820000031
Y-the aromatic carboxylic acid anion represented by (a) is at least one selected from the group consisting of anions represented by the following formulae (15-1) to (15-9):
Figure FDA0002708832820000032
。
2. the block copolymer of claim 1, which is an a-B type block copolymer.
3. The block copolymer according to claim 1, wherein a content of the structural unit derived from the vinyl monomer having an acidic group in 100% by mass of the A block is 2% by mass to 20% by mass.
4. The block copolymer according to claim 1, wherein the content of the structural unit represented by the general formula (1) in 100% by mass of the B block is 30% by mass to 85% by mass.
5. The block copolymer according to any one of claims 1 to 4, wherein the content of the A block in 100% by mass of the block copolymer is 35% by mass to 85% by mass.
6. A first composition comprising the block copolymer according to any one of claims 1 to 5.
7. The first composition of claim 6, wherein the molecular weight distribution PDI of the block copolymer is 2.0 or less.
8. A second composition obtained by washing the first composition according to claim 7 with water and drying.
9. A dispersant comprising the block copolymer according to any one of claims 1 to 5, the first composition according to claim 6 or 7 or the second composition according to claim 8.
10. A pigment-dispersion composition comprising the dispersant of claim 9, a pigment and a dispersion solvent.
11. The pigment-dispersion composition according to claim 10, which is used for a color filter.
12. A method for producing the block copolymer according to any one of claims 1 to 5, comprising:
a step (A) for preparing a precursor of a block copolymer, wherein the precursor of the block copolymer has an A block and a B block, the A block contains a structural unit derived from a vinyl monomer having an acidic group, and the B block contains a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (3);
a step (B) of obtaining a block copolymer by allowing an alkali metal salt of at least one member selected from the group consisting of aromatic dicarboxylic acid imides, aromatic sulfonic acids, aromatic phosphonic acids, and aromatic carboxylic acids to act on a precursor of the block copolymer obtained in the step (A),
Figure FDA0002708832820000041
in the formula (2), R21And R22Each independently represents a chain or ring-like hydrocarbon group which may have a substituent, R21And R22Can bond with each other and form a cyclic structure; x2Represents a divalent linking group; r23Represents a hydrogen atom or a methyl group,
Figure FDA0002708832820000042
in the formula (3), R31、R32And R33Each independently represents a chain or ring-like hydrocarbon group which may have a substituent, R31、R32And R33Two or more of them may bond with each other and form a cyclic structure; x3Represents a divalent linking group; r34Represents a hydrogen atom or a methyl group; x-Represents a halogen anion, and is a halogen anion,
in the step (B),
the alkali metal salt of the aromatic dicarboxylic acid imide used is at least one selected from the group consisting of alkali metal salts represented by the following formulae (6-1) to (6-7):
Figure FDA0002708832820000051
in the above formulae (6-1) to (6-7), M1Represents an alkali metal;
the alkali metal salt of the aromatic sulfonic acid used is at least one selected from the group consisting of alkali metal salts represented by the following formulae (7-1) to (7-9):
Figure FDA0002708832820000052
in the above formulae (7-1) to (7-9), M2Represents an alkali metal;
the alkali metal salt of an aromatic phosphonic acid used is at least one selected from the group consisting of alkali metal salts represented by the following formulae (8-1) to (8-7):
Figure FDA0002708832820000061
in the above formulae (8-1) to (8-7), M3Represents an alkali metal;
the alkali metal salt of the aromatic carboxylic acid used is at least one selected from the group consisting of alkali metal salts represented by the following formulae (9-1) to (9-9):
Figure FDA0002708832820000062
in the above formulae (9-1) to (9-9), M4Represents an alkali metal.
13. The method for producing a block copolymer according to claim 12, wherein in the step (A), a precursor of the block copolymer is prepared by living radical polymerization.
14. The method for producing a block copolymer according to claim 12 or 13, further comprising a step (C) of washing the block copolymer obtained in the step (B) with water.
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